Substituted 4-(2-nitro-4-phenoxy-sulfonylanilino)phenylazopyrazoles

ABSTRACT

Dyes of the formula   AND MIXTURES THEREOF, WHEREIN R1 is hydroxy or amino, R2 is hydrogen, alkyl of 1 to 4 carbon atoms, cyclohexyl, phenyl, tolyl or benzyl, R3 is hydrogen, methyl, carbamoyl, methoxycarbonyl or ethoxycarbonyl, and R4 is hydrogen, methyl or methoxy, ARE SPARINGLY SOLUBLE IN WATER AND ARE HIGHLY SUITABLE FOR DYEING AND PRINTING FIBRES, YARNS AND TEXTILES CONSISTING OF SYNTHETIC OR REGENERATED ORGANIC MATERIALS OF HIGH MOLECULAR WEIGHT AND HYDROPHOBIC CHARACTER.

United States Patent 1191 Altermatt May 20, 1975 SUBSTITUTED 4-( 2-NITRO-4-PHENOXY- SULFONYLANILINO)- PHENYLAZOPYRAZOLES [7 5] Inventor: Ruedi Altermatt, Buckten,

Basel-Land, Switzerland Related U.S. Application Data Continuation-impart of Ser. No. 74,924, Sept. 23,,

1970, Pat. No. 3,741,954.

[30] Foreign Application Priority Data Oct. 21, 1969 Switzerland 15709/69 May 16, 1973 Switzerland 6967/73 52 U.S. c1 260/162; 8/26; 8/410;

260/163; 260/456 A; 260/505' R; 260/543 R 51 Int. Cl. c0911 29/38; D06p 3/54 58 Field of Search 260/162, 163

[56] References Cited UNITED STATES PATENTS 2,879,269 3/1959 Merian 260/205 X 3,136,752 6/1964 Jung et al. 260/163 X 3,344,133 9/1967 Bossard et al. 260/163 FOREIGN PATENTS OR APPLICATIONS 770,598 10/1967 Canada 260/162 Primary Examiner-Floyd D. Higel Assistant Examiher-C. F. Warren Attorney, Agent, or Firm-Gerald D. Sharkin; Richard E. Vila; Melvyn A. Kassenofi' 5 7 ABSTRACT Dyes of thef orinula N0 and mixtures thereof,

wherein R is hydroxy or amino, R is hydrogen, alkyl of l to 4 carbon atoms,

cyclohexyl, phenyl, tolyl or benzyl, R is hydrogen, methyl, carbamoyl,

methoxycarbonyl or ethoxycarbonyl, and R, is hydro'gemmethyl or methoxy, are sparingly soluble in water and are highly suitable for dyeing and printing fibres, yarns and textiles consisting of synthetic or regenerated organic materials of high molecular weight and hydrophobic character.

13-Claims, No Drawings tate, magnesium or calcium oxide.

SUBSTITUTED F 4-(2-NITRO-4-PHENOXY- SULFONYLANILINO)PHENYLAZOPYRAZOLES This application is a continuation-in-part of application Ser. No. 74,924, filed Sept. "23, 1970, now; US. Pat. No. 3,741,954.

Y The new compounds have the formula 3 I N N=NA@*NH--SO2O R N Hal so Hal where Hal represents a chlorine or bromine atom, with one mole of a phenol of the formula and subsequently with one mole of an amine of the formula (III) N N NH The condensation reaction generally takes place in an inert solvent, such as water, ethanol, n-butanol, benzyl alcohol, ethylene glycol, polyethylene glycol, benzene, toluene, xylene or chlorobenzene at temperatures in the range of 25C to 200C It is usually of advantage to add to the reaction mixture an agent which binds acid, such as an alkali carbonate, bicarbonate or ace- The halogen atom bound to the S0 group in th component of formula (II) is more highly reactive than the halogen atom bound to the nucleus; accordingly the initially added phenol of formula (III) is bound to the S0 group and the amine of formula (IV)'directly to the nucleus B. It is of advantage to carryout the'first step of the reaction at temperatures below 100C and the second step at about C to 200C, if necessary in an autoclave.

The compounds of formula (I) can also be obtained by condensing one mole of a sulphonic acid of the formula Hal SO.,H

where Hal represents a chlorine or bromine atom, with one mole of an amine of formula (IV), converting the resulting compound into the sulphonic acid chloride of the formula 3 N N N@ NH so c1 T I (VII) and condensing this with one mole of a phenol of formula (Ill).

The condensation of the compound of formula (VI) with the amine of formula (IV), preferably in one of the aforenamed solvents, is carried out at temperatures in the range of about 80C to 2009C, while the condensation of the compound of formula (Vll) with the phenol of formula (III) is effected preferably in the same reaction medium at-temperatures of 25C to C.

The compoundof formula (I) can be produced by another route comprising diazotization of a compound of the formula (VIII),

and coupling of the resulting compoundwith a com- The diazotizing and coupling reactions have been known for more than a hundred years (P. Griess, Liebigs Ann. Chem. 137, 30, 1866) and are the most frequently performed reactions in the, chemistry of dyes,

so there is no necessity to describe them in greater detail.

Excellent properties as dyes are shown by mixtures of compounds of formula (I). These mixtures can be pro duced by reacting one mole of a compound of the formula N N NH' R2N with one mole of a mixture of different compounds of the formula Hal@ so or by reacting one mole of a mixture of different compounds of the formula with one mole of a compound of the formula Ha1{/;}So,- 0 7.

It is advantageous to convert the new dyes, produced as given in the foregoing, into dyeing preparations before application to the fibre. For this purpose standard methods are used, such as grinding in the presence of dispersing agents and/or fillers. The mixtures are dried in a vacuum or spray drier to give dry preparations.

. After the addition of a suitable volume of water, they can be exhaust dyed, pad dyed or printed from long or short bath as required.

From aqueous dispersion the dyes'build up powerfully on fibres, yarns and textiles consisting of synthetic or regenerated organic materials of high molecular weight and hydrophobic character. They are especially suitable for dyeing and printing polyester, cellulose diacetate, cellulose triacetate and polyamide fibres and textiles of these fibres. They are also applicable to polyolefin fibres.

The known dyeing and printing methods are used, for example the process described in French Pat. No. 1,445,371. r

The dyeings obtained are of yellow shade and show high fastness to thermofixation, pleatingand sublimation, gas fumes, cross dyeing,.dry cleaning, ozone, chlorine, and to wet treatments, suchas water, washing and perspiration. They are stable to the pre-cure and postcure permanent press finishing processes, are well dischargeable and show a good reserve of wool, rayon, silk and cotton. The light fastness is excellent, evenin pale shades, which makes the dyes highly suitable as components for the production of fashionable pastel shades.

grade.

" EXAMPLE 1 39.9 Parts of the compound of the formula go -a o NO CH 3 2 and 6 parts of sodium hydroxide are dissolved in 600 parts of water and the solution is mixed with a solution of 7 parts of sodium nitrite in 20 parts of water. The resulting solution is dropped into a mixture of parts of water, 100 parts of ice and 35 parts of 35 hydrochloric acid. Stirring is continued for 3 hours at 0-5, then the excess sodium nitrite is decomposed with 0.5 part of aminosulphonic acid. The diazonium salt solution thus formed is dropped slowly at O5 into a solution of 17.4 parts of l-phenyl-3-methyl-5 pyrazolone, 6 parts of sodium hydroxide and 8 parts of sodium carbonate in 100 parts of water and 50 parts of ice. The coupling mixture is stirred for 3-4 hours at 05, after which time the newly formed dye is filtered, washed with water and dried. The pure dye of the formula gives yellow dyeings on synthetic fibres which have excellent fastness properties.

EXAMPLE 2 41.5 parts of a compound of the formula ocH N0 and 6 parts of sodium hydroxide are dissolved in 600 parts of water. A solution containing 7 parts of sodium nitrite in 20 parts of water is added to the first solution. The resulting solution is fed slowly, over a period of 30 to 45minutes, into a well-stirred mixture containing 50 partsofwater, parts of ice and'35 parts of 35 hydrochloric acid. After this, the mixture is stirred for a further3 to hours at a temperature of 0 to 5, at the stuff is almost completely precipitated. The precipitate is filtered off, washed with water and dried. The pure dvestuff has the following formula OCH and dyes synthetic fibres in yellow tones with outstanding fastness properties.

EXAMPLE 3 38.5 parts of a compound of the formula and 6 parts of sodium hydroxide are dissolved in 600 35 parts of water. A solution containing 7 parts of sodium nitrite in 20 parts of water is added to the first solution. The resulting solution is fed over a period of to 45 minutes into a well-stirred mixture containing 50 parts of water, 200 parts of ice and parts of 35 hydrochloric acid.

After this, the mixture is stirred for a further 3 to 4 hours at a temperature of 0 to 5, at the end of which time the excess sodium nitrite is decomposed by the addition of 0.5 part of aminosulphonic acid.

The diazonium salt solution so obtained is fed slowly into a mixture containing 17.4 parts of lphenyl-3- methyl-5-aminopyrazol, 200-parts of glacial acetic acid and 100 parts of ice. The reaction mixture is buffered with sodium acetate to a pH value of 2.5 to 3.5, and further stirred for l to 2 hours at a temperature of 0 to 5 until the reaction is completed. The precipitated dyestuff is then filtered off, after which the residual acid is washed out with water and the product is dried. It has the formula The pure dyestuff dyes synthetic fibres in yellow tones I it and 3919 parts-of the compound of the formula with outstanding fastness properties.

1 5 cn N o-so NH N=N NH o as I c11 N EXAMPLE 4 A mixture containing 31.4-parts of the phenyl ester of l-chloro-2-nitrobenzene-4-sulphonic acid, 32.8 parts of the (3'-methyl)-phenyl ester of l-chloro-2- nitrobenzene-4-sulphonic acid, and 58.4 parts of the compound'of the formula 300 parts of ethyl alcohol, parts of water andr l0 parts of magnesium oxide, is heated with stirring in an autoclave at a temperature of to .for .24 hours. The reaction mixture is then allowed to cool to 30 with vigorous stirring, afterwhich the crystallised dyestuff mixture isfiltered off, washed first with 200 parts of cold ethyl alcohol and then with hot water, and finally dried. The dyestuff mixture so obtained dyes synthetic fibres in yellow tones with outstanding fastness properties and comprises the following components:

EXAMPLE 5 38.5 parts of the compound of the formula H C -YO SO Q NH NH plus 12 parts of sodium hydroxide are dissolved ml 200 parts of water. To this first solution a second solution of 14 parts sodium nitrite in 40 parts of water is added. The resulting solution is added dropwise with thorough stirring over a period of 30 to 45 minutes to a mixture of 100 parts of water, 400 parts ice and 70 parts of 35 hydrochloric acid. After this, the mixture is stirred for a further 3 to 4 hours at a temperature of to at the end of which time the excess sodium nitrite is decomposed by the addition of 1 part of aminosulphonic acid. The diazonium salt solution so obtained is fed slowly, over a period of 30 minutes into a solution containing 25 parts of 1-isopropy1-5aminopyrazo1, 400 parts of glacial acetic acid and .300-parts of ice. The reaction mixture is buffered with sodium-acetate-to a pH value of 2.5 to 3.5, and further stirred for-1 to 2 hours at a temperature of 0 to 5 until the'reaction is completed. The precipitated dyestuff mixture thus obtained comprises the following two components:

N0 NR CH The dyestuff mixture is filtered off, washed with water and then dried. lt dyes synthetic fibres in yellow tones with outstanding fastness properties.

EXAMPLE 6 1 19.7 parts of a compound of the formula wo ho s 1,800 parts of water. A solution containing 21 parts of sodium nitrite in 60 parts of water is added to this first solution. The resulting solution is fed over a period of 30 to 45 minutes into a well-stirred mixture containing 150 parts of water, 600 parts of ice and 105 parts of 35 hydrochloric acid. After this, the mixture is stirred for a further 3 to 4 hours at a temperature of 0 to 5,

at the end of which time the excess sodium nitrite is de-' composed by the addition of 1.5 parts of aminosulphonic acid. The diazonium salt solution so obtained is and 18 parts of sodium hydroxide are dissolved in slowly fed over a period of 30 to 45 minutes into a solution containing 16.5 parts of l-cyclohexyl-S- aminopyrazol, 17.3 parts of 1-benzyl-5-aminopyrazol and 13.9 parts of 1-isopropy1-3-methyl-5-aminopyrazo1 and dyes synthetic fibres in yellow tones with outstanding fastness properties.

EXAMPLE 7 A mixture containing 38.5 parts of a compound of the formula I H5C6-O-S02@ NH@ NR2 and 39.9 parts of a compound of the formula is diazotized in an analogous manner to that used for Example 5. The diazonium salt solution so obtained is fed over a period of 1 hour at a temperature of 0 to 5- and ' Y CH3 I N=N o-so m. I

Application Example 1 and 20 parts of an emulsion of a chlorinated benzene. 100 parts of a fabric of polyester fibre are entered into this dy eba'th at 2025. The temperature is increased to l00 in about 30 minutes and the fabric dyed for l hour'at this temperature. It is then removed, rinsed, soaped for 15 minutes at 70 with a 0.1 solution of an alkylphenylpolyglycolether, rinsed again and dried. A reddish yellow dyeing, having excellent fastness properties, is obtained. i

Application Example 2 v A mixture of 3O parts of the dye produced as in Example 2, 40 parts of sodium dinaphthylmethanedisulphonate, 50 parts of sodium cetylsulphate and 50 parts of anhydrous sodium sulphate is ground in a ball mill for 48 hours to give a fine powder. 4 Parts of the powder are dispersed in 1,000 parts of water at 4050.

Parts of a scoured fabric of polyester fibre are entered into the bath and, after slow heating to the fabric is dyed for about 1 hour at this temperature under pressure. On removal it is rinsed, soaped, rinsed and dried. A reddish yellow dyeing with excellent fastness properties is obtained. H

Application Example 3 A fine aqueous dispersion of 30 parts of the heterogenous dye produced as in Example 4, 70 parts of sodium dinaphthylmethanedisulphonate and 3 parts of sodium alginate is made up to 1000 parts with water and stirred well. A polyester fabric is padded with this liquor at 20, air dried at 60100 and treated for 1 minute in dry heat at 230 for fixation of the dyeing. The fabric is then rinsed, soaped, rinsed again and dried. A level reddish-yellow dyeing with good fastness properties is obtained; 7

The dyes listed in the following table correspond to the formula R -"N I 0 TABLE 4 have the formulae 7 l q I 3 N O a s,

N 2 NR Example 3',"

the mixture dyestuffs of the formulae I v z. CH

a c -o-so NH N=N I: t N c and Example 4 and the mixture of dyestuffs of the formulae What we claim is: 1. A compound of the formula wherein R is hydroxy or amino, R is hydrogen, alkyl of l to 4 carbon atoms, cyclohexyl, phenyl, tolyl or benzyl,

4. A compound according to claim 1 wherein R is cyclohexyl.

5. A compound according to claim 1 wherein R is tolyl.

'6. A compound according to claim 1 wherein R is methoxycarbonyl or ethoxycarbonyl. I

7. A compound according to ,claim 1 wherein R; is hydrogen.

8. A compound according to claim 1 wherein R is methyl or methoxy and is in the 3-position.

9. The compound according to claim 1 having the formula 10. The compound according to claim 1 having the formula cn I 4 l N o-so @-N=N l Ill-C 3 0 on 7 CH3 2 11. The compound according to claim 1 having the formula v a 0-50 NH-@-N= CECE H o I 3 12. The compound according to claim 1 having the formula 13. The compound according to claim 1 having the formula 

1. A COMPOUND OF THE FORMULA
 2. A compound according to claim 1 wherein R2 is hydrogen, alkyl of 1 to 4 carbon atoms, phenyl or benzyl, and R3 is hydrogen, methyl or carbamoyl.
 3. A compound according to claim 2 wherein R4 is methyl or methoxy.
 4. A compound according to claim 1 wherein R2 is cyclohexyl.
 5. A compound according to claim 1 wherein R2 is tolyl.
 6. A compound according to claim 1 wherein R3 is methoxycarbonyl or ethoxycarbonyl.
 7. A compound according to claim 1 wherein R4 is hydrogen.
 8. A compound according to claim 1 wherein R4 is methyl or methoxy and is in the 3-position.
 9. The compound according to claim 1 having the formula
 10. The compound according to claim 1 having the formula
 11. The compound according to claim 1 having the formula
 12. The compound according to claim 1 having the formula
 13. The compound according to claim 1 having the formula 